Eveline H Tiekink, Ron Verdijk, Trevor A Hamlin, F Matthias Bickelhaupt
{"title":"Organocatalyzed Diels-Alder Reactions: Unexplored Hydrogen Bond Donor Catalysts.","authors":"Eveline H Tiekink, Ron Verdijk, Trevor A Hamlin, F Matthias Bickelhaupt","doi":"10.1002/cplu.202500081","DOIUrl":null,"url":null,"abstract":"<p><p>We have quantum chemically investigated the catalytic effect of hydrogen bonding organocatalysts, (H<sub>2</sub>N)<sub>2</sub>C=X (X=O, S, Se, NH, PH, AsH, CH<sub>2</sub>, SiH<sub>2</sub> GeH<sub>2</sub>), such as urea, on the classic Diels-Alder reaction. All studied hydrogen bond donor catalysts enhance the Diels-Alder reaction between acrolein and 1,3-butadiene to a similar extent. Our activation strain and Kohn-Sham molecular orbital analyses show that these organocatalysts lower the reaction barrier by polarizing the π-orbitals away from the reactive carbon atoms of acrolein, reducing the Pauli repulsion between the reactants. Interestingly, this catalytic mechanism is not limited to >C=X moieties with relatively electronegative X (e. g., O, S, NH) but extends to situations like >C=CH<sub>2</sub> and even >C=SiH<sub>2</sub>.</p>","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":" ","pages":"e202500081"},"PeriodicalIF":3.0000,"publicationDate":"2025-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"ChemPlusChem","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1002/cplu.202500081","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
We have quantum chemically investigated the catalytic effect of hydrogen bonding organocatalysts, (H2N)2C=X (X=O, S, Se, NH, PH, AsH, CH2, SiH2 GeH2), such as urea, on the classic Diels-Alder reaction. All studied hydrogen bond donor catalysts enhance the Diels-Alder reaction between acrolein and 1,3-butadiene to a similar extent. Our activation strain and Kohn-Sham molecular orbital analyses show that these organocatalysts lower the reaction barrier by polarizing the π-orbitals away from the reactive carbon atoms of acrolein, reducing the Pauli repulsion between the reactants. Interestingly, this catalytic mechanism is not limited to >C=X moieties with relatively electronegative X (e. g., O, S, NH) but extends to situations like >C=CH2 and even >C=SiH2.
期刊介绍：
ChemPlusChem is a peer-reviewed, general chemistry journal that brings readers the very best in multidisciplinary research centering on chemistry. It is published on behalf of Chemistry Europe, an association of 16 European chemical societies.
Fully comprehensive in its scope, ChemPlusChem publishes articles covering new results from at least two different aspects (subfields) of chemistry or one of chemistry and one of another scientific discipline (one chemistry topic plus another one, hence the title ChemPlusChem). All suitable submissions undergo balanced peer review by experts in the field to ensure the highest quality, originality, relevance, significance, and validity.
求助内容：
应助结果提醒方式：
京公网安备 11010802042870号
